U.S. patent number 7,422,735 [Application Number 09/604,001] was granted by the patent office on 2008-09-09 for use of crosslinked cationic polymers in skin cosmetic and dermatological preparations.
This patent grant is currently assigned to BASF Aktiengesellschaft. Invention is credited to Reinhold Dieing, Michael Gotsche, Peter Hossel, Axel Sanner, Kristin Tiefensee, Katrin Zeitz.
United States Patent |
7,422,735 |
Hossel , et al. |
September 9, 2008 |
**Please see images for:
( Certificate of Correction ) ** |
Use of crosslinked cationic polymers in skin cosmetic and
dermatological preparations
Abstract
The invention relates to the use of at least one copolymer
obtainable by (i) free-radically initiated copolymerization of a
monomer mixture comprising (a) 1 to 99.99% by weight of at least
one monomer chosen from N-vinylimidazoles and diallylamines
optionally in partially or completely quaternized form; (b) 0 to
98.99% by weight of at least one neutral or basic water-soluble
monomer which is different form (a); (c) 0 to 50% by weight of at
least one unsaturated acid or unsaturated anhydride, (d) 0 to 50%
by weight of at least one free-radically copolymerizable monomer
which is different from (a), (b) or (c); and (e) 0.01 to 10% by
weight of at least one monomer which acts as crosslinker and has at
least two ethylenically unsaturated, nonconjugated double bonds;
and (ii) subsequent partial or complete quaternization or
protonation of the polymer in the case where the monomer (a) is
unquaternized or only partially quaternized, as additive for skin
cosmetic and dermatological preparations.
Inventors: |
Hossel; Peter (Schifferstadt,
DE), Tiefensee; Kristin (Westheim, DE),
Sanner; Axel (Frankenthal, DE), Dieing; Reinhold
(Schifferstadt, DE), Gotsche; Michael (Aachen,
DE), Zeitz; Katrin (Ludwigshafen, DE) |
Assignee: |
BASF Aktiengesellschaft
(Ludwigshafen, DE)
|
Family
ID: |
7912928 |
Appl.
No.: |
09/604,001 |
Filed: |
June 26, 2000 |
Foreign Application Priority Data
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Jun 29, 1999 [DE] |
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199 29 758 |
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Current U.S.
Class: |
424/70.15;
514/937; 526/264; 424/78.24; 424/78.22; 424/78.03; 424/47 |
Current CPC
Class: |
A61K
8/8194 (20130101); C08F 8/44 (20130101); A61P
17/16 (20180101); A61K 8/8182 (20130101); A61K
8/817 (20130101); A61Q 19/00 (20130101); C08F
8/44 (20130101); C08F 226/00 (20130101); A61K
2800/5426 (20130101); A61Q 19/10 (20130101); Y10S
514/937 (20130101) |
Current International
Class: |
A61K
8/81 (20060101); A61K 8/00 (20060101); A61K
31/74 (20060101); A61K 31/785 (20060101); C08F
26/10 (20060101); A61K 31/79 (20060101) |
Field of
Search: |
;424/70.15,78.03,47,78.22,78.24 ;526/304,264 ;514/937 |
References Cited
[Referenced By]
U.S. Patent Documents
Foreign Patent Documents
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2151770 |
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Dec 1995 |
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CA |
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544 158 |
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May 1993 |
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DE |
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42 13 971 |
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Nov 1993 |
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DE |
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196 26 657 |
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Jan 1998 |
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DE |
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197 31 907 |
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Jan 1999 |
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DE |
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197 49 618 |
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May 1999 |
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DE |
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687 694 |
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Dec 1995 |
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EP |
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893 117 |
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Jan 1999 |
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EP |
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913 143 |
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May 1999 |
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EP |
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WO 93/22358 |
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Nov 1993 |
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WO |
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WO 93/25595 |
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Dec 1993 |
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WO |
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WO 96/26229 |
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Aug 1996 |
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WO |
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WO 96/37525 |
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Nov 1996 |
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WO |
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WO 97/35544 |
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Oct 1997 |
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WO |
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Primary Examiner: Hartley; Michael G.
Assistant Examiner: Fubara; Blessing M
Attorney, Agent or Firm: Novak Druce + Quigg LLP
Claims
We claim:
1. In a skin cosmetic or dermatological preparation selected from
cosmetic compositions for cleansing the skin, cosmetic compositions
for the care and protection of the skin, nail care compositions,
and preparations for decorative cosmetics, the improvement wherein
the composition consists essentially of customary additives and at
least one copolymer obtained by (i) free-radically initiated
copolymerization of a monomer mixture comprising (a) 1 to 99.99% by
weight of at least one monomer selected from the group consisting
of N-vinylimidazoles and diallylamines, optionally in partially or
completely quaternized form; (b) 0 to 98.99% by weight of at least
one neutral or basic water-soluble monomer which is different from
(a); (c) 0 to 40% by weight of at least one unsaturated acid or
unsaturated anhydride, (d) 0 to 50% by weight of at least one
free-radically copolymerizable monomer which is different from the
monomers (a), from the monomers (b) and from the monomers (c); and
(e) 0.01 to 10% by weight of at least one monomer which acts as
crosslinker and has at least two ethylenically unsaturated,
nonconjugated double bonds; and (ii) subsequent partial or complete
quaternization and protonation of the polymer in the case where the
monomer (a) is unquaternized or only partially quaternized.
2. The preparation as claimed in claim 1, wherein the protonation
as in (ii) takes place during formulation of the preparation.
3. The preparation as claimed in claim 1, wherein monomer (a) is at
least one diallylamine derivative of the formula (II), ##STR00003##
in which the radical R.sup.4 is C.sub.1-C.sub.24 alkyl.
4. The preparation as claimed in claim 1, wherein monomer (a) is at
least one N-vinylimidazole derivative of the formula (I),
##STR00004## in which the radicals R.sup.1 to R.sup.3 independently
of one another are hydrogen, C.sub.1-C.sub.4-alkyl or phenyl.
5. The preparation as claimed in claim 1, wherein monomer (b) is at
least one N-vinyllactam.
6. The preparation as claimed in claim 1, selected from the group
consisting of cosmetic compositions for cleansing the skin.
7. The preparation as claimed in claim 6, selected from the group
consisting of soaps, syndets, liquid washing, shower and bath
preparations.
8. The preparation as claimed in claim 1, selected from the group
consisting of cosmetic compositions for the care and protection of
the skin, nailcare compositions, and preparations for decorative
cosmetics.
9. The preparation as claimed in claim 8, selected from the group
consisting of skincare compositions, personal hygiene care
compositions, footcare compositions, sunscreens, repellents,
shaving compositions, depilatories, anti-acne compositions, makeup,
mascara, lipsticks, eyeshadows, kohl pencils, eyeliners, blushers,
powders and eyebrow pencils.
10. The preparation as claimed in claim 9, wherein the skincare
compositions are selected from the group consisting of water-in-oil
or oil-in-water skin creams, day and night creams, eye creams,
antiwrinkle creams, moisturizers, bleaching creams, vitamin creams,
skin lotions, care lotions and moisturizing lotions.
11. The preparation as claimed in claim 1, wherein the copolymer is
used in the form of a water-in-oil emulsion.
12. The preparation as claimed in claim 11, wherein the copolymer
has been polymerized in the emulsion or suspension.
13. The preparation as claimed in claim 12, wherein the oil phase
of the emulsion or suspension comprises a cosmetic oil.
14. The skin composition or dermatological preparation of claim 1
wherein a monomer mixture consisting of (a) 1 to 99.99% by weight
of at least one monomer selected from the group consisting of
N-vinylimidazoles and diallylamines, optionally in partially or
completely quaternized form; (b) 0 to 98.99% by weight of at least
one neutral or basic watersoluble monomer which is different from
(a); (d) 0 to 50% by weight of at least one free-radically
copolymerizable monomer which is different from the monomers (a),
from the monomers (b), and from unsaturated acids and unsaturated
anhydrides; (e) 0.01 to 10% by weight of at least one monomer which
acts as crosslinker and has at least two ethylenically unsaturated,
nonconjugated double bonds; is employed in the free-radical
initiated copolymerization stage (i).
15. The skin composition or dermatological preparation of claim 1
wherein a monomer mixture consisting of (a) 1 to 99.99% by weight
of at least one monomer selected from the group consisting of
N-vinylimidazoles and diallylamines, optionally in partially or
completely quaternized form; (b) 0 to 98.99% by weight of at least
one neutral or basic water-soluble monomer which is different from
(a); (c) 0 to 40% by weight of at least one unsaturated acid or
unsaturated anhydride, (d) 0 to 50% by weight of at least one
free-radically copolymerizable monomer which is different from the
monomers (a), from the monomers (b) and from the monomers (c); and
(e) 0.01 to 10% by weight of at least one monomer which acts as
crosslinker and has at least two ethylenically unsaturated,
nonconjugated double bonds; is employed in the free-radical
initiated copolymerization stage (i).
Description
The present invention relates to the use of crosslinked cationic
copolymers in skincare compositions, and to skincare compositions
which comprise at least one of these copolymers.
Cationic polymers are frequently used as conditioners in hair
cosmetic formulations. They primarily serve to improve the wet
combability of hair. Furthermore, cationic polymers prevent the
electrostatic charging of hair.
Thus, for example, EP-A-0 246 580 describes the use of
uncrosslinked homo- and copolymers of 3-methyl-1-vinylimidazolium
chlorides in cosmetic compositions. EP-A-0 544 158 and U.S. Pat.
No. 4,859,756 claim the use of uncrosslinked homo- and copolymers
of chloride-free, quaternized N-vinylimidazoles in cosmetic
preparations. EP-A-0 715 843 discloses the use of uncrosslinked
copolymers of a quaternized N-vinylimidazole, N-vinylcaprolactam
and N-vinylpyrrolidone, and optionally a further comonomer in
cosmetic preparations.
DE-A-28 21 239 (U.S. Pat. No. 4,348,380) describes copolymers of
quaternized diallylammonium compounds in hair cosmetic
preparations. The polymers are uncrosslinked.
DE-A-31 06 974 describes a hair-treatment composition of the
pre-shampooing type, which comprises uncrosslinked homo- and
copolymers of quaternized diallylammonium compounds.
U.S. Pat. No. 5,275,809, EP-A-0 522 755, EP-A-0 521 665 and EP-A-0
521 666 disclose copolymers containing dimethyldiallylammonium
chloride for use in shampoos. In none of the abovementioned
specifications is a crosslinked polymer described.
U.S. Pat. No. 4,806,345 describes crosslinked cationic thickeners
for cosmetic formulations comprising quaternized dimethylaminoethyl
methacrylate and acrylamide.
WO 93/25595 describes crosslinked cationic copolymers based on
quaternized dialkylaminoalkyl acrylates or
dialkylaminoalkyl-acrylamides. A proposed application is the use of
these crosslinked copolymers as thickeners in cosmetic
preparations. A process for the preparation of water-soluble or
water-swellable polymers in a W/O emulsion is claimed in EP-A-0 126
528, which comprises polymerizing the water-soluble monomers in the
presence of emulsifiers with the addition of a particular
dispersion system consisting of alkanols. Cationic comonomers,
inter alia, are also used. The oil phases are aliphatic and
aromatic hydrocarbons or higher aliphatic esters. The polymers are
not intended for cosmetics applications.
DE-A-197 49 618 describes anionic copolymers which are prepared in
cosmetic oils in inverse suspension polymerization and used
directly in cosmetic formulations.
DE-A-32 09 224 describes the preparation of crosslinked polymers
based on N-vinylpyrrolidone and (quaternized) N-vinylimidazole.
These polymers are claimed for use as adsorbents and ion
exchangers.
Crosslinked, agglomerated vinylimidazole copolymers are mentioned
in WO 96/26229 as dye-transfer inhibitors. They are highly
crosslinked, water-insoluble and virtually unswellable, and are
therefore not suitable as conditioners or gel formers in cosmetic
formulations.
U.S. Pat. No. 4,058,491 discloses crosslinked cationic hydrogels
comprising N-vinylimidazole or N-vinylpyrrolidone and a quaternized
basic acrylate and other comonomers. These gels are proposed for
the complexation and controlled relief of anionic active
substances.
WO 96/37525 describes the preparation of crosslinked copolymers of,
inter alia, N-vinylpyrrolidone and quaternized vinylimidazoles in
the presence of polymerization regulators, and their use, in
particular, in detergents. The compounds are unsuitable as gel
formers.
DE-A-42 13 971 describes copolymers of an unsaturated carboxylic
acid, quaternized vinylimidazole and optionally further monomers
and a crosslinker. The polymers are proposed as thickeners and
dispersants.
The method of thickening by protonation of a water-soluble,
crosslinked aminoalkyl(meth)acrylate is described in EP-A-0 624 617
and EP-A-0 027 850.
The use of copolymers comprising an aminoalkyl (meth)acrylate in
cosmetics is described in EP-A-0 671 157. However, the polymers
mentioned therein are exclusively used for joint use with setting
or conditioning polymers.
WO 97/35544 describes the use of crosslinked cationic polymers
comprising dialkylaminoalkyl (meth)acrylates or dialkylaminoalkyl
(meth)acrylamides in shampoo compositions.
EP-A-0 893 117 describes the use of high molecular weight cationic
polymers which comprise bi- or polyfunctional monomers, as
conditioning agents in hair cosmetic preparations.
DE-A-197 31 907 describes the use of crosslinked cationic
copolymers which comprise N-vinylimidazoles, in hair cosmetic
formulations.
It is an object of the present invention then to provide new types
of cosmetic compositions which permit improved skin care.
We have found that this object is achieved using the crosslinked
cationic copolymers known from DE-A-19 731 764 or EP-A-0 893 117
and DE-A-197 31 907 and proposed therein for the treatment of
hair.
The invention firstly relates to the use of crosslinked copolymers
obtainable by (i) free-radically initiated copolymerization of a
monomer mixture comprising (a) 1 to 99.99% by weight, preferably 2
to 94.98% by weight, particularly preferably 10 to 70% by weight,
of at least one monomer chosen from N-vinylimidazoles and
diallylamines, optionally in partially or completely quaternized
form; (b) 0 to 98.99% by weight, preferably 5 to 97.98% by weight,
particularly preferably 20 to 89.95% by weight, of at least one
neutral or basic water-soluble monomer which is different from (a),
(c) 0 to 50% by weight, preferably 0 to 40% by weight, particularly
preferably 0 to 30% by weight, of at least one unsaturated acid or
unsaturated anhydride, (d) 0 to 50% by weight, preferably b to 40%
by weight, particularly preferably 0 to 30% by weight, of at least
one free-radically copolymerizable monomer which is different from
(a), (b) and (c), and (e) 0.01 to 10% by weight, preferably 0.02 to
8% by weight, particularly preferably 0.05 to 5% by weight, of at
least one bi- or polyfunctional free-radically copolymerizable
monomer, and (ii) subsequent partial or complete quaternization or
protonation of the resulting copolymer where monomer (a) is an
unquaternized or only partially quaternized monomer, as additive
for skin cosmetic and dermatological preparations.
Suitable monomers (a) are the N-vinylimidazole derivatives of the
formula (I),
##STR00001## in which the radicals R.sup.1 to R.sup.3 independently
of one another are hydrogen, C.sub.1-C.sub.4-alkyl or phenyl.
Also suitable are diallylamines of the formula (II),
##STR00002## in which R.sup.4 is C.sub.1-C.sub.24-alkyl.
The copolymers according to the invention have the advantage over
the copolymers used in accordance with the prior art and based on
N,N-dialkylaminoalkyl (meth)acrylates or
N,N-dialkylaminoalkyl(meth)acrylamide that they do not hydrolyze in
aqueous solution and are therefore particularly stable.
Examples of compounds of the formula (I) are given in Table 1
below:
TABLE-US-00001 TABLE 1 R.sup.1 R.sup.2 R.sup.3 H H H Me H H H Me H
H H Me Me Me H H Me Me Me H Me Ph H H H Ph H H H Ph Ph Me H Ph H Me
Me Ph H H Ph Me H Me Ph Me H Ph Me = methyl Ph = phenyl
Other monomers of the formula (I) which can be used are the ethyl,
propyl or butyl analogs of the methyl-substituted l-vinylimidazoles
listed in Table 1.
Examples of compounds of the formula (II) are diallylamines, in
which R.sup.4 is methyl, ethyl, iso- or n-propyl, iso-, n- or
tert-butyl, pentyl, hexyl, heptyl, octyl, nonyl or decyl. Examples
of longer-chain radicals R.sup.4 are undecyl, dodecyl, tridecyl,
pentadecyl, octadecyl and icosyl.
The monomers (a) can either be used in quaternized form as monomers
or be polymerized in nonquaternized form, where, in the latter
case, the resulting copolymer is either quaternized or
protonated.
Compounds which are suitable for quaternizing the compounds of the
formulae (I) and (II) are, for example, alkyl halides having from 1
to 24 carbon atoms in the alkyl group, e.g. methyl chloride, methyl
bromide, methyl iodide, ethyl chloride, ethyl bromide, propyl
chloride, hexyl chloride, dodecyl chloride, lauryl chloride and
benzyl halides, in particular benzyl chloride and benzyl bromide.
Other suitable quaternizing agents are Dialkyl sulfates, in
particular dimethyl sulfate or diethyl sulfate. The quaternization
of the basic monomers of the formulae (I) and (II) can also be
carried out using alkylene oxides, such as ethylene oxide or
propylene oxide, in the presence of acids.
The quaternization of the monomer or of a polymer using one of said
quaternizing agents can be carried out by methods which are
generally known.
The quaternization of the copolymer can take place completely or
else only partially. The proportion of quaternized monomers (a) in
the copolymer can vary over a wide range and is, for example, from
about 20 to 100 mol %.
Preferred quaternizing agents are methyl chloride, dimethyl sulfate
or diethyl sulfate.
Preferred examples of monomers (a) are 3-methyl-1-vinylimidazolium
chloride and methosulfate, and dimethyldiallylammonium
chloride.
Particularly preferred monomers (a) are 3-methyl-1-vinylimidazolium
chloride and methosulfate.
Compounds which are suitable for the protonation are, for example,
mineral acids, such as HCl, H.sub.2SO.sub.4, H.sub.3PO.sub.4, and
monocarboxylic acids, such as, for example, formic acid and acetic
acid, dicarboxylic acids and polyfunctional carboxylic acids, such
as, for example, oxalic acid and citric acid, and all other
proton-donating compounds and substances which are able to
protonate the corresponding vinylimidazole or diallylamine. In
particular, water-soluble acids are suitable for the
protonation.
The polymer can be protonated either after the polymerization or
during the formulation of the cosmetic composition, during which,
as a rule, a physiologically compatible pH is set.
The term "protonation" means that at least some of the protonatable
groups of the polymer, preferably 20 to 100 mol %, are protonated,
resulting in an overall cationic charge of the polymer.
Suitable monomers (b) which are different from (a) are
N-vinyllactams, such as, for example, N-vinylpiperidone,
N-vinylpyrrolidone and N-vinylcaprolactam, N-vinylacetamide,
N-methyl-N-vinylacetamide, acrylamide, methacrylamide,
N,N-dimethylacrylamide, N-methylolmethacrylamide,
N-vinyloxazolidone, N-vinyltriazole, hydroxyalkyl(meth)acrylates,
such as for example, hydroxyethyl (meth)acrylate and hydroxypropyl
(meth)acrylates, or alkyl ethylene glycol(meth)acrylates having
from 1 to 50 ethylene glycol units in the molecule. Also suitable
are dialkylaminoalkyl (meth)acrylates and
dialkylaminoalkyl(meth)acrylamides, such as, for example,
N,N'-dimethylaminoethylmethacrylate or
N-[3-(dimethylamino)propyl]methacrylamide.
Preference is given to using N-vinyllactams as monomers (b). Very
particular preference is given to N-vinylpyrrolidone.
Compounds which are suitable as monomers (c) are unsaturated
carboxylic acids and unsaturated anhydrides, such as, for example,
acrylic acid, methacrylic acid, crotonic acid, itaconic acid,
maleic acid, fumaric acid or their corresponding anhydrides,
unsaturated sulfonic acids, for example
acrylamidomethylpropanesulfonic acid, and the salts of the
unsaturated acids, such as, for example, the alkali metal or
ammonium salts.
Compounds suitable as monomers (d) are C.sub.1-C.sub.40-alkyl
esters of (meth)acrylic acid, where the esters are derived from
linear, branched-chain or carbocyclic alcohols, e.g. methyl
(meth)acrylate, ethyl (meth)acrylate, tert-butyl (meth)acrylate,
isobutyl (meth)acrylate, n-butyl (meth)acrylate, stearyl
(meth)acrylate, or esters of alkoxylated fatty alcohols, e.g.
C.sub.1-C.sub.40-fatty alcohols reacted with ethylene oxide,
propylene oxide or butylene oxide, in particular
C.sub.10-C.sub.18-fatty alcohols reacted with 3 to 150 ethylene
oxide units. Also suitable are N-alkyl-substituted acrylamides
containing linear, branched-chain or carbocyclic alkyl radicals,
such as N-tert-butylacrylamide, N-butylacrylamide,
N-octylacrylamide, and N-tert-octylacrylamide.
Also suitable are styrene, and vinyl and allyl esters of
C.sub.1-C.sub.40-carboxylic acids which can be linear,
branched-chain or carbocyclic, e.g. vinyl acetate, vinyl
propionate, vinyl neononanoate, vinyl neoundecanoic acid, vinyl
t-butyl benzoate, alkyl vinyl ethers, for example methyl vinyl
ether, ethyl vinyl ether, butyl vinyl ether and stearyl vinyl
ether.
Acrylamides, such as N-tert-butylacrylamide, N-butylacrylamide,
N-octylacrylamide, N-tert-octylacrylamide and N-alkyl-substituted
acrylamides containing linear, branched-chain or carbocyclic alkyl
radicals, where the alkyl radical can have the meanings given above
for R.sup.4.
Monomers (e), which have a crosslinking function, are compounds of
at least two ethylenically unsaturated, nonconjugated double bonds
in the molecule.
Suitable crosslinkers are, for example, acrylic esters, methacrylic
esters, allyl ethers or vinyl ethers of at least dihydric alcohols.
The OH groups of the parent alcohols can be completely or partially
etherified or esterified; however, the crosslinkers contain at
least two ethylenically unsaturated groups.
Examples of the parent alcohols are dihydric alcohols, such as
1,2-ethanediol, 1,2-propanediol, 1,3-propanediol, 1,2-butanediol,
1,3-butanediol, 2,3-butanediol, 1,4-butanediol, but-2-ene-1,4-diol,
1,2-pentanediol, 1,5-pentanediol, 1,2-hexanediol, 1,6-hexanediol,
1,10-decanediol, 1,2-dodecanediol, 1,12-dodecanediol, neopentyl
glycol, 3-methylpentane-1,5-diol, 2,5-dimethyl-1,3-hexanediol,
2,2,4-trimethyl-1,3-pentanediol, 1,2-cyclohexanediol,
1,4-cyclohexanediol, 1,4-bis(hydroxymethyl)cyclohexane,
mononeopentyl glycol hydroxylpivolate,
2,2-bis(4-hydroxyphenyl)propane,
2,2-bis[4-(2-hydroxypropyl)phenyl]propane, diethylene glycol,
triethylene glycol, tetraethylene glycol, dipropylene glycol,
tripropylene glycol, tetrapropylene glycol, 3-thiopentane-1,5-diol,
and also polyethylene glycols, polypropylene glycols and
polytetrahydrofurans each having molecular weights of from 200 to
10,000. As well as the homopolymers of ethylene oxide or propylene
oxide, it is also possible to use block copolymers of ethylene
oxide or propylene oxide or copolymers which contain incorporated
ethylene oxide and propylene oxide groups. Examples of parent
alcohols having more than two OH groups are trimethylolpropane,
glycerol, pentaerythritol, 1,2,5-pentanetriol, 1,2,6-hexanetriol,
triethoxycyanuric acid, sorbitan, sugars, such as sucrose, glucose
and mannose. It is of course also possible to use the polyhydric
alcohols following reaction with ethylene oxide or propylene oxide
and as the corresponding ethoxylates or propoxylates respectively.
The polyhydric alcohols can also be first converted into the
corresponding glycidyl ethers by reaction with epichlorohydrin.
Other suitable crosslinkers are the vinyl esters or the esters of
monohydric, unsaturated alcohols with ethylenically unsaturated
C.sub.3- to C.sub.6-carboxylic acids, for example acrylic acid,
methacrylic acid, itaconic acid, maleic acid or fumaric acid.
Examples of such alcohols are allyl alcohol, 1-buten-3-ol,
5-hexen-1-ol, 1-octen-3-ol, 9-decen-1-ol, dicyclopentenyl alcohol,
10-undecen-1-ol, cinnamyl alcohol, citronellol, crotyl alcohol or
cis-9-octadecen-1-ol. It is, however, also possible to esterify the
monohydric, unsaturated alcohols using polybasic carboxylic acids,
for example malonic acid, tartaric acid, trimellitic acid, phthalic
acid, terephthalic acid, citric acid or succinic acid.
Other suitable crosslinkers are esters of unsaturated carboxylic
acids with the above-described polyhydric alcohols, for example
oleic acid, crotonic acid, cinnamic acid or 10-undecanoic acid.
Also suitable as monomers (e) are straight-chain or branched,
linear or cyclic, aliphatic or aromatic hydrocarbons which have at
least two double bonds, which in the case of aliphatic hydrocarbons
must not be conjugated, e.g. divinyl benzene, divinyl toluene,
1,7-octadiene, 1,9-decadiene, 4-vinyl-1-cyclohexene,
trivinylcyclohexane or polybutadienes having molecular weights from
200 to 20,000.
Other suitable crosslinkers are acrylamides, methacrylamides and
N-allylamines of at least difunctional amines. Such amines are, for
example, 1,2-diaminomethane, 1,2-diaminoethane, 1,3-diaminopropane,
1,4-diaminobutane, 1,6-diaminohexane, 1,12-dodecanediamine,
piperazine, diethylenetriamine or isophoronediamine. Also suitable
are the amides of allylamine and unsaturated carboxylic acids such
as acrylic acid, methacrylic acid or itaconic acid, maleic acid, or
at least dibasic carboxylic acids as described above.
Other suitable crosslinkers are triallylamine and
triallylmonoalkylammonium salts, e.g. triallylmethylammonium
chloride or methylsulfate.
Other suitable crosslinkers are N-vinyl compounds of urea
derivatives, at least difunctional amides, cyanurates or urethanes,
for example of urea, ethyleneurea, propyleneurea, or tartramide,
e.g. N,N'-divinylethyleneurea or N,N'-divinylpropyleneurea.
Further suitable crosslinkers are divinyldioxane, tetrallylsilane
or tetravinylsilane.
Preference is given to using crosslinkers which are soluble in the
monomer mixture.
Particularly preferred crosslinkers are, for example,
pentaerythritol triallyl ether, methylenebisacrylamide,
triallylamine and triallylalkylammonium salts, divinylimidazole,
N,N'-divinylethyleneurea, reaction products of polyhydric alcohols
with acrylic acid or methacrylic acid, methacrylic esters and
acrylic esters of polyalkyleneoxides or polyhydric alcohols which
have been reacted with ethylene oxide and/or propylene oxide and/or
epichlorohydrin.
Very particularly preferred crosslinkers are pentaerythritol
triallyl ether, methylenebisacrylamide, N,N'-divinylethyleneurea,
triallylamine and acrylic esters of glycol, butanediol,
trimethylolpropane or glycerol or acrylic esters of glycol,
butanediol, trimethylolpropane or glycerol reacted with ethylene
oxide and/or epichlorohydrin.
Each of the monomers (a) to (e) can be used individually or in a
mixture with other monomers of the same group.
The polymers are prepared by the processes of free-radically
initiated polymerization known per se, e.g. by solution
polymerization, emulsion polymerization, suspension polymerization,
precipitation polymerization, inverse suspension polymerization,
inverse emulsion polymerization or by polymerization in
supercritical media, e.g. supercritical carbon dioxide, without
being limited thereto.
The polymerization is usually carried out at temperatures of from
20.degree. C. to 150.degree. C. and at atmospheric pressure or
under autogenous pressure; the temperature can be kept constant or
be increased continuously or discontinuously, e.g. in order to
increase the conversion.
Initiators which can be used for the free-radical polymerization
are the water-soluble and water-insoluble peroxo and/or azo
compounds customary for this purpose, for example alkali metal or
ammonium peroxodisulfates, dibenzoylperoxide, tert-butyl
perpivalate, tert-butyl-per-2-ethylhexanoate, di-tert-butyl
peroxide, tert-butyl hydroperoxide, azobisisobutyronitrile,
azobis(2-amidinopropane) dihydrochloride or
2,2'-azobis(2-methylbutyronitrile). Also suitable are initiator
mixtures or redox initiator systems, such as, for example, ascorbic
acid/iron(II) sulfate/sodium peroxodisulfate, tert-butyl
hydroperoxide/sodium disulfite, tert-butyl hydroperoxide/sodium
hydroxymethanesulfinate. The initiators can be used in the
customary amounts, for example, 0.05 to 5% by weight, or 0.05 to
0.3 mol %, based on the amount of monomers to be polymerized.
If the copolymers used according to the invention are prepared in
inverse suspension polymerization in cosmetic oils, the oil phase
chosen according to the invention is a component which has a
positive effect on the cosmetic formulation (appearance, feel on
the skin). Such components are, for example, native oils, such as
sunflower oil, almond oil, avocado oil, wax esters such as jojoba
oil, fatty acid isopropyl esters such as isopropyl palmitate,
isopropyl myristate, di- and triglycerides of fatty acids, such as,
for example, caprylic/capric glycerides. The oil phase proportion
in the overall emulsion is 15 to 70% by weight, preferably 20 to
35% by weight.
In order to disperse the water phase in the organic phase, W/O
emulsifiers known for this purpose are used. The HLB value of the
emulsifiers used is between 4 and 8 [HLB
value=hydrophilic/lipophilic balance, cf. W. C. Giffin, J. Soc.
Cosmet. Chem. 1, (1950) 311]. Such emulsifiers are, for example,
sorbitan monooleate, sorbitan monostearate, glyceryl monostearate,
block copolymers of hydroxy fatty acid polyesters and
polyoxyethylene. They can be used alone or in combination in
overall concentrations of from 2 to 10% by weight, preferably from
2 to 5% by weight, based on the total emulsion.
It is also possible to add emulsifiers with a HLB value of greater
than 8 to the emulsion, specifically in concentrations of from 0.25
to 7% by weight, based on the total emulsion. Such emulsifiers are,
for example, ethoxylated C.sub.6-C.sub.12-nonylphenols and
C.sub.12-C.sub.18 fatty alcohols; the degree of ethoxylation is 5
to 20 mol %.
The emulsification of the aqueous phase into the oil phase does not
require any special units; the aqueous monomer phase can be
emulsified in a standard polymerization vessel by stirring, e.g.
with an anchor stirrer. The rate of rotation is between 30 and 400
rpm, depending on the geometry of the tank.
Following the polymerization, water-in-oil emulsions are obtained
which have a solids content of from 10 to 40% by weight, preferably
from 15 to 35% by weight. To increase the solid content, the
emulsions can be partially or completely dewatered by
distillation.
The W/O emulsions of crosslinked polymers prepared according to the
invention are used as thickeners, preferably in skin cosmetic or
dermatological applications. The polymers are not isolated, but
used directly in the form of the W/O emulsion. The thickening
action of the W/O emulsion takes place immediately after the W/O
emulsion has been mixed with a cosmetic O/W emulsion; in order to
achieve the optimum effect, no addition of an inversion agent is
necessary. Purely aqueous systems can also be thickened. This gives
a cream gel.
The molecular weight and the K value of the copolymers used
according to the invention can be varied within a wide range in a
manner known per se through the choice of polymerization
conditions, for example polymerization time, polymerization
temperature or initiator concentration, and by the content of
crosslinker. The K-values of preferred copolymers are in a range
between 30 and 350, preferably 50 and 350.
The K values are measured in accordance with Fikentscher,
Cellulosechemie, Vol. 13, pp. 58-64 (1932) at 25.degree. C. 0.1%
strength in 0.5 molar sodium chloride solution.
If the degrees of crosslinking are high, the K values for the
polymers can not be determined.
The polymers according to the invention can be used in skin
cosmetic and dermatological preparations.
For example, the polymers according to the invention are used in
cosmetic compositions for cleansing the skin. Such cosmetic
cleansers are chosen from bar soaps, such as toilet soaps, curd
soaps, transparent soaps, luxury soaps, deodorant soaps, cream
soaps, baby soaps, skin-protection soaps, abrasive soaps and
syndets, liquid soaps, such as pasty soaps, soft soaps and washing
pastes, and liquid wash, shower and bath preparations, such as
washing lotions, shower preparations and gels, foam baths, oil
baths and scrub preparations.
The polymers according to the invention are preferably used in
cosmetic compositions for the care and protection of the skin, in
nailcare compositions, and in preparations for decorative
cosmetics.
Particular preference is given to the use in skincare compositions,
personal hygiene care compositions, footcare compositions,
sunscreens, repellants, shaving compositions, depilatories,
anti-acne compositions, makeup, mascara, lipsticks, eyeshadows,
kohl pencils, eye liners, blushers, powders and eyebrow
pencils.
The skincare compositions are, in particular, in the form of W/O or
O/W skin creams, day and night creams, eye creams, face creams,
antiwrinkle creams, moisturizing creams, bleaching creams, vitamin
creams, skin lotions, care lotions and moisturizing lotions.
In the cosmetic and dermatological preparations the polymers
according to the invention can develop particular effects. The
polymers can, inter alia, contribute to the moisturizing and
conditioning of the skin and to improving the feel of the skin. The
polymers can also act as thickeners in the formulations. The
addition of the polymers according to the invention can, in certain
formulations, achieve a considerable improvement in skin
tolerability.
The copolymers according to the invention are present in the skin
cosmetic and dermatological preparations in an amount of from about
0.001 to 20% by weight, preferably 0.01 to 10% by weight very
particularly preferably 0.1 to 5% by weight, based on the total
weight of the composition.
Depending on the area of application, the compositions according to
the invention can be applied in a form suitable for skincare, such
as, for example, as cream, foam, gel, stick, powder, mousse, milk
or lotion.
In addition to containing the polymers according to the invention
and suitable solvents, the skin cosmetic preparations can also
comprise additives customary in cosmetics, such as emulsifiers,
preservatives, perfume oils, cosmetic active ingredients, such as
phytantriol, Vitamin A, E and C, retinol, bisabolol, panthenol,
sunscreens, bleaching agents, colorants, tinting agents, tanning
agents (e.g. dihydroxyacetone), collagen, protein hydrolysates,
stabilizers, pH regulators, dyes, salts, thickeners, gel formers,
bodying agents, silicones, moisturizers, refatting agents and other
customary additives.
Suitable solvents which can be mentioned in particular are water
and lower monoalcohols or polyols having from 1 to 6 carbon atoms
or mixtures thereof; preferred monoalcohols or polyols are ethanol,
isopropanol, propylene glycol, glycerol and sorbitol.
Other customary additives which may be present are fatty
substances, such as mineral and synthetic oils, such as, for
example, paraffins, silicone oils and aliphatic hydrocarbons having
more than 8 carbon atoms, animal and vegetable oils, such as, for
example, sunflower oil, coconut oil, avocado oil, olive oil,
lanolin, or waxes, fatty acids, fatty acid esters, such as, for
example, triglyerides of C.sub.6-C.sub.30-fatty acids, wax esters,
such as, for example, jojoba oil, fatty alcohols, vaseline,
hydrogenated lanolin and acetylated lanolin. It is of course also
possible to use mixtures thereof.
Customary thickeners in formulations of this type are crosslinked
polyacrylic acids and derivatives thereof, polysaccharides such as
xanthan gum, agar agar, alginates or tyloses,
carboxymethylcellulose or hydroxycarboxymethylcellulose, fatty
alcohols, monoglycerides and fatty acids, polyvinyl alcohol and
polyvinylpyrrolidone.
The polymers according to the invention can also be mixed with
traditional polymers if specific properties are to be set.
Suitable traditional polymers are, for example, anionic, cationic,
amphoteric and neutral polymers.
Examples of anionic polymers are homo- and copolymers of acrylic
acid and methacrylic acid or salts thereof, copolymers of acrylic
acid and acrylamide and salts thereof; sodium salts of
polyhydroxycarboxylic acids, water-soluble or water-dispersible
polyesters, polyurethanes and polyureas. Particularly suitable
polymers are copolymers of t-butyl acrylate, ethyl acrylate,
methacrylic acid (e.g. Luvimer.RTM. 100P), copolymers of ethyl
acrylate and methacrylic acid (e.g. Luvimer.RTM. MAE), copolymers
of N-tert-butylacrylamide, ethyl acrylate, acrylic acid
(Ultrahold.RTM. 8, strong), copolymers of vinyl acetate, crotonic
acid and optionally further vinyl esters (e.g. Luviset.RTM.
grades), maleic anhyride copolymers, optionally reacted with
alcohols, anionic polysiloxanes, e.g. carboxyfunctional ones,
copolymers of vinylpyrrolidone, t-butyl acrylate, methacrylic acid
(e.g. Luviskol.RTM. VBM), copolymers of acrylic acid and
methacrylic acid with hydrophobic monomers, such as, for example,
C.sub.4-C.sub.30-alkyl esters of (meth)acrylic acid,
C.sub.4-C.sub.30-alkylvinyl esters, C.sub.4-C.sub.30-alkyl vinyl
ethers and hyaluronic acid.
Further suitable polymers are cationic polymers with the INCI name
polyquaternium, e.g. copolymers of
vinylpyrrolidone/N-vinylimidazolium salts (Luviquat.RTM. FC,
Luviquat.RTM. HM, Luviquat.RTM. MS, Luviquat.RTM. Care), copolymers
of N-vinylpyrrolidone/dimethylaminoethyl methacrylate, quaternized
with diethylsulfate (Luviquat.RTM. PQ 11), copolymers of
N-vinylcaprolactam/N-vinylpyrrolidone/N-vinylimidazolium salts
(Luviquat.RTM. Hold); cationic cellulose derivatives
(polyquaternium-4 and 10), acrylamide copolymers (polyquaternium-7)
and chitosan.
Also suitable as further polymers are neutral polymers, such as
polyvinylpyrrolidones, copolymers of N-vinylpyrrolidone and vinyl
acetate and/or vinyl propionate, polysiloxanes,
polyvinylcaprolactam and copolymers containing N-vinylpyrrolidone,
polyethylenimines and salts thereof, polyvinylamines and salts
thereof, cellulose derivatives, polyaspartic acid salts and
derivatives.
To set certain properties, the preparations can additionally also
comprise conditioning substances based on silicone compounds.
Suitable silicone compounds are, for example, polyalkylsiloxanes,
polyarylsiloxanes, polyarylalkylsiloxanes, polyether siloxanes or
silicone resins.
The copolymers according to the invention are used in cosmetic or
dermatological preparations, the preparation of which is carried
out in accordance with the customary principles familiar to the
person skilled in the art.
Such formulations are advantageously in the form of emulsions,
preferably as water-in-oil (W/O) or oil-in-water (O/W) emulsions.
According to the invention, it is, however, also possible and in
some cases advantageous to choose other types of formulation, for
example hydrodispersions, gels, oils, oleogels, multiple emulsions,
for example in the form of W/O/W or O/W/O emulsions, anhydrous
ointments or ointment bases etc.
The emulsions which can be used according to the invention are
prepared by known methods.
In addition to the copolymer according to the invention, the
emulsions comprise customary constituents, such as fatty alcohols,
fatty acid esters and, in particular, fatty acid triglycerides,
fatty acids, lanolin and derivatives thereof, natural or synthetic
oils or waxes and emulsifiers in the presence of water.
The choice of emulsion-type-specific additives and the preparation
of suitable emulsions is described, for example, in Schrader,
Grundlagen und Rezepturen der Kosmetika [Cosmetic bases and
formulations], Huthig Buch Verlag, Heidelberg, 2nd Edition, 1989,
third part, to which reference is expressly made here.
Thus, a skin cream which can be used according to the invention
can, for example, be in the form of a W/O emulsion. An emulsion of
this type comprises an aqueous phase which is emulsified in an oil
or fatty phase using a suitable emulsifier system.
The concentration of the emulsifier system in this type of emulsion
is about 4 to 35% by weight, based on the total weight of the
emulsion; the fatty phase constitutes about 20 to 60% by weight,
and the aqueous phases about 20 to 70% by weight, in each case
based on the total weight of the emulsion. The emulsifiers are
those which are customarily used in this type of emulsion. They
are, for example, chosen from: C.sub.12-C.sub.18 sorbitan fatty
acid esters; esters of hydroxystearic acid and C.sub.12-C.sub.30
fatty alcohols; mono- and diesters of C.sub.12-C.sub.18 fatty acids
and glycerol or polyglycerol; condensates of ethylene oxide and
propylene glycols; oxypropylenated/oxyethylenated C.sub.12-C.sub.20
fatty alcohols; polycyclic alcohols, such as sterols; aliphatic
alcohols having a high molecular weight, such as lanolin; mixtures
of oxypropylenated/polyglycerolated alcohols and magnesium
isostearate; succinyl esters of polyoxyethylenated or
polyoxypropylenated fatty alcohols; and mixtures of magnesium,
calcium, lithium, zinc or aluminum lanolate and hydrogenated
lanolin or lanolin alcohol.
Suitable fatty components which can be present in the fatty phase
of the emulsions include hydrocarbon oils, such as paraffin oil,
purcellin oil, perhydrosqualene and solutions of microcrystalline
waxes in these oils; animal or vegetable oils, such as sweet almond
oil, avocado oil, calophylum oil, lanolin and derivatives thereof,
castor oil, sesame oil, olive oil, jojoba oil, Karite oil,
Hoplostethus oil, mineral oils whose distillation start point under
atmospheric pressure is at about 250.degree. C. and whose
distillation end point is at 410.degree. C., such as, for example,
vaseline oil; esters of saturated or unsaturated fatty acids, such
as alkyl myristates, e.g., isopropyl, butyl or cetyl myristate,
hexadecyl stearate, ethyl or isopropyl palmitate, octanoic or
decanoic triglycerides and cetyl ricinoleate.
The fatty phase can also comprise silicone oils which are soluble
in other oils, such as dimethylpolysiloxane,
methylphenylpolysiloxane and the silicone glycol copolymer, fatty
acids and fatty alcohols.
In order to favor the retention of oils, it is also possible to use
waxes, such as, for example, carnauba wax, candellila wax, beeswax,
microcrystalline wax, ozokerite wax and Ca, Mg and Al oleates,
myristates, linoleates and stearates.
These water-in-oil emulsions are generally prepared by adding the
fatty phase and the emulsifier to the batch container. These are
then heated at a temperature of from 70 to 75.degree. C., then the
oil-soluble ingredients are added and, with stirring, water is
added which has been heated beforehand to the same temperature and
in which the water-soluble ingredients have been dissolved
beforehand; the mixture is stirred until an emulsion of the desired
fineness is obtained, which is then left to cool to room
temperature, if necessary with gentle stirring.
A care emulsion according to the invention can also be in the form
of an O/W emulsion. An emulsion of this type usually comprises an
oil phase, emulsifiers which stabilize the oil phase in the water
phase, and an aqueous phase, which is usually in thickened
form.
The aqueous phase of the O/W emulsion of the preparations according
to the invention optionally comprises alcohols, diols or polyols
and ethers thereof, preferably ethanol, isopropanol, propylene
glycol, glycerol, ethylene glycol monoethyl ether; customary
thickeners or gel formers, such as, for example, crosslinked
polyacrylic acids and derivatives thereof, polysaccharides, such as
xantham gum or alginates, carboxymethylcellulose of
hydroxycarboxymethylcellulose, fatty alcohols, polyvinyl alcohol
and polyvinylpyrrolidone.
The oil phase comprises oil components which are customary in
cosmetics, such as, for example: esters of saturated and/or
unsaturated, branched and/or unbranched C.sub.3-C.sub.30-alkane
carboxylic acids and saturated and/or unsaturated, branched and/or
unbranched C.sub.3-C.sub.30-alcohols, of aromatic carboxylic acids
and saturated and/or unsaturated, branched and/or unbranched
C.sub.3-C.sub.30-alcohols, for example, isopropylmyristate,
isopropyl stearate, hexyldecylstearate, oleyloleate; and also
synthetic, semisynthetic and natural mixtures of such esters, such
as jojoba oil; branched and/or unbranched hydrocarbons and
hydrocarbon waxes; silicone oils, such as cyclomethicone,
dimethylpolysiloxane, diethylpolysiloxane,
octamethylcyclotetrasiloxne and mixtures thereof; dialkyl ethers;
mineral oils and mineral waxes; triglycerides of saturated and/or
unsaturated, branched and/or unbranched
C.sub.8-C.sub.24-alkanecarboxylic acids; they can be chosen from
synthetic, semisynthetic or natural oils, such as olive oil, palm
oil, almond oil or mixtures.
Suitable emulsifiers are, preferably, O/W emulsifiers, such as
polyglycerol esters, sorbitan esters or partially esterified
glycerides.
The preparation can be carried out by melting the oil phase at
about 80.degree. C.; the water-soluble constituents are dissolved
in hot water, then slowly and with stirring added to the oil phase;
the mixture is then homogenized and stirred until cold.
The copolymers according to the invention are also suitable for use
in washing and shower gel formulations, and also bath
preparations.
In addition to the polymers according to the invention, such
formulations usually comprise anionic surfactants as base
surfactants, and amphoteric and nonionic surfactants as
cosurfactants, and also lipids, perfume oils, dyes, organic acids,
preservatives and antioxidants, and thickeners/gel formers, skin
conditioning agents and moisturizers.
In the wash, shower and bath preparations it is possible to use all
anionic, neutral, amphoteric or cationic surfactants which are
customarily used in body-cleansing compositions.
The formulations comprise from 2 to 50% by weight of surfactants,
preferably from 5 to 40% by weight, particularly preferably from 8
to 30% by weight.
Suitable anionic surfactants are, for example, alkyl sulfates,
alkylether sulfates, alkylsulfonates, alkylaryl sulfonates, alkyl
succinates, alkyl sulfosuccinates, N-alkoylsarcosinates, acyl
taurates, acyl isethionates, alkyl phosphates, alkyl ether
phosphates, alkyl ether carboxylates, alpha-olefinsulfonates, in
particular the alkali metal and alkaline earth metal salts, e.g.
sodium, potassium, magnesium, calcium, and ammonium and
triethanolamine salts. The alkyl ether sulfates, alkyl ether
phosphates and alkyl ether carboxylates can have between 1 and 10
ethylene oxide or propylene oxide units, preferably 1 to 3 ethylene
oxide units, in the molecule.
Suitable examples of sodium lauryl sulfate, ammonium lauryl
sulfate, sodium lauryl ether sulfate, ammonium lauryl ether
sulfate, sodium lauryl sarcosinate, sodium oleyl succinate,
ammonium lauryl sulfosuccinate, sodium dodecylbenzene sulfonate,
triethanolamine dodecylbenzenesulfonate.
Suitable amphoteric surfactants are, for example, alkylbetaines,
alkylamidopropylbetaines, alkylsulfobetaines, alkylglycinates,
alkylcarboxyglycinates, alkylamphoacetates or -propionates,
alkylamphodiacetates or -dipropionates.
For example, cocodimethylsulfopropylbetaine, lauryl betaine,
cocamidopropylbetaine or sodium cocamphopropionate can be used.
Suitable nonionic surfactants are, for example, the reaction
products of aliphatic alcohols or alkylphenols having 6 to 20
carbon atoms in the alkyl chain which can be linear or branched,
with ethylene oxide and/or propylene oxide. The amount of alkylene
oxide is about 6 to 60 moles per mole of alcohol. Also suitable are
alkylamine oxides, mono- and dialkylalkanolamides, fatty acid
esters of polyethylenenglycols, ethoxylated fatty acids amides,
alkyl polyglycosides or sorbitan ether esters.
In addition, the wash, shower and bath preparations can comprise
customary cationic surfactants, such as, for example, quaternary
ammonium compounds, for example cetyltrimethylammonium
chloride.
In addition, it is also possible to use further customary cationic
polymers, such as, for example, copolymers of acrylamide and
dimethyldiallylammonium chloride (polyquaternium-7), cationic
cellulose derivatives (polyquaternium-4, -10), guar
hydroxypropyltrimethylammonium chloride (INCI: Hydroxypropyl Guar
Hydroxypropyltrimonium Chloride), copolymers of N-vinylpyrrolidone
and quaternized N-vinylimidazole (polyquaternium-16, -44, -46),
copolymers of N-vinypyrrolidone/dimethylaminoethyl methacrylate,
quaternized with diethylsulfate (polyquaternium-11) and others.
Furthermore, the wash and shower gel formulations and bath
preparations can comprise thickeners, such as, for example, sodium
chloride, PEG-55, propylene glycol oleates, PEG-120 methyl glucose
dioleates and others and also preservatives, further active
ingredients and auxiliaries and water.
A PREPARATION OF THE POLYMERS
Preparation Example 1
A stirred apparatus was charged with 400 g of water and 46 g of
dimethyldiallylammonium chloride solution (65% strength). 10% of
Feed 1, consisting of 270 g of N-vinylpyrrolidone and 0.6 g of
N,N'-divinylethyleneurea, were added to this initial charge. The
mixture was heated to 60.degree. C. with stirring in a stream of
nitrogen, and Feed 1 was metered in over the course of 3 hours, and
Feed 2 consisting of 0.9 g of
2,2'-azobis(2-amidinopropane)-dihydrochloride in 100 g of water,
was metered in over the course of 4 hours. After 3 hours, the
mixture was diluted with 700 g of water and stirred for a further
hour. Then, 1.5 g of 2,2'-azobis(2-amidinopropane)dihydrochloride
in 30 g of water were added and the mixture was stirred for a
further 2 hours at 60.degree. C. This gave a colorless
high-viscosity polymer solution with a solids content of 20.9% and
a K value of 80.3.
Preparation Example 2
A stirred apparatus was charged with 300 g of Feed 1, consisting of
200 g of N-vinylpyrrolidone, 77 g of dimethyldiallylammonium
chloride solution (65% strength), 1.13 g of
N,N'-divinyl-ethyleneurea and 440 g of water, and the mixture was
heated to 60.degree. C. with stirring in a stream of nitrogen. The
remainder of Feed 1 was metered in over 2 hours and Feed 2,
consisting of 0.75 g of
2,2'-azobis(2-amidinopropane)dihydrochloride in 100 g of water, was
metered in over 4 hours. When the addition of Feed 1 was complete,
the reaction mixture was diluted with 1620 g of water. When the
addition of Feed 2 was complete, the mixture was stirred for a
further hour at 60.degree. C., then 1.25 g of
2,2'-azobis(2-amidino-propane)dihydrochloride in 65 g of water were
added and the mixture was stirred for a further hour. This gave a
colorless high-viscosity polymer solution with a solids content of
10.2% and a K value of 80.
Preparation Example 3
A stirred apparatus was charged with 130 g of water and 48 g of
3-methyl-1-vinylimidazolium chloride, and the mixture was heated to
60.degree. C. with stirring in a stream of nitrogen. Then, Feed 1,
consisting of 192 g of N-vinylpyrrolidone, 0.48 g of
N,N'-divinylethyleneurea and 450 g of water, was metered in over 3
hours, and Feed 2, consisting of 1.44 g of
2,2'-azobis(2-amidinopropane)dihydrochloride in 80 g of water, was
metered in over 4 hours. The mixture was then stirred for a further
hour at 60.degree. C. In order to keep the mixture stirrable, it
was diluted with a total of 2100 g of water as required. This gave
a colorless high-viscosity polymer solution with a solids content
of 8.2% and a K value of 105.
Preparation Example 4
716 g of water were charged to a stirred apparatus and, with
stirring and in a stream of nitrogen, heated to 60.degree. C. Then,
Feed 1, consisting of 180 g N-vinylpyrrolidone, 20 g of
3-methyl-1-vinylimidazolium methylsulfate, 0.32 g of
N,N'-divinylethyleneurea and 25 g of water, was metered in over 2
hours, and Feed 2, consisting of 0.6 g of
2,2'-azobis-(2-amidinopropane)dihydrochloride in 60 g of water, was
metered in over 3 hours. When the addition of Feed 1 was complete,
the reaction mixture was diluted with 1000 g of water. Following
the addition of Feed 2, the mixture was stirred for a further 3
hours at 70.degree. C. This gives a colorless high-viscosity
polymer solution with a solids content of 11.0% and a K value of
86.
Preparation Example 5
440 g of water were charged to a stirred apparatus and, with
stirring and in a stream of nitrogen, heated to 60.degree. C. Then,
Feed 1, consisting of 180 g of N-vinylpyrrolidone, 20 g of
3-methyl-1-vinylimidazolium methylsulfate, 0.30 g of
N,N'-divinylethylene-urea and 25 g of water, was metered in over 2
hours, and Feed 2, consisting of 0.6 g of
2,2'-azobis(2-amidinopropane)dihydro-chloride in 60 g of water, was
metered in over 3 hours. Following the addition of Feed 2, the
mixture was stirred for a further 3 hours at 70.degree. C. In order
to keep the reaction mixture stirrable, it was diluted with a total
of 1275 g of water as required. This gave a colorless
high-viscosity polymer solution with a solids content of 11.3% and
a K value of 105.
Preparation Example 6
650 g of water were charged to a stirred apparatus and, with
stirring and in a stream of nitrogen, heated to 60.degree. C. Then,
Feed 1, consisting of 225 g of N-vinylpyrrolidone, 25 g of
2,3-dimethyl-1-vinylimidazolium methylsulfate, 0.25 g of
N,N'-divinylethyleneurea and 580 g of water, was metered in over 3
hours, and Feed 2, consisting of 0.7 g of
2,2'-azobis-(2-amidinopropane)dihydrochloride in 100 g of water,
was metered in over 4 hours. When the addition of Feed 1 was
complete, the reaction mixture was diluted with 835 g of water.
Following the addition of Feed 2, the mixture was stirred for a
further hour, and 1.25 g of
2,2'-azobis(2-amidinopropane)dihydrochloride in 77 g of water were
then added. The mixture was then stirred for a further 2 hours at
70.degree. C. This gave a colorless high-viscosity polymer solution
with a solids content of 10.4% and a K value of 106.
Preparation Example 7
650 g of water were charged to a stirred apparatus and, with
stirring and in a stream of nitrogen, heated to 60.degree. C. Then,
Feed 1, consisting of 225 g of N-vinypyrrolidone, 25 g of
2,3-dimethyl-1-vinylimidazolium methylsulfate, 0.375 g of
N,N'-divinylethyleneurea and 580 g of water, was metered in over 3
hours, and Feed 2, consisting of 0.7 g of
2,2'-azobis-(2-amidinopropane)dihydrochloride in 100 g of water,
was metered in over 4 hours. After the addition of Feed 1 was
complete, the reaction mixture was diluted with 1135 g of water.
Following the addition of Feed 2, the mixture was stirred for a
further hour, and 1.25 g of
2,2'-azobis(2-amidinopropane)dihydrochloride in 77 g of water were
then added. The mixture was then stirred for a further 2 hours at
70.degree. C. This gave a colorless high-viscosity polymer solution
with a solid content of 9.2% and a K value of 92.
Preparation Example 8
800 g of cyclohexane, 5 g of sorbitan monooleate, 5 g of Hypermer
B246 (Hypermer B246: polymeric surfactant from ICI) and 1 g of
2,2'-azobis(2,4-dimethylvaleronitrile) were heated to 65.degree. C.
in a reaction vessel with nitrogen blanketing. The feed, consisting
of 100 g of 3-methyl-1-vinylimidazolium methylsulfate, 100 g of
N-vinylpyrrolidone, 100 g of water and 0.25 g of tripropylene
glycol diacrylate, was metered in over the course of 20 minutes.
The mixture was then stirred for 6 hours at 65.degree. C. 200 g of
cyclohexane were then added, and the water was distilled off
azeotropically, and the polymer was filtered off and dried. The K
value of an aqueous solution of the polymer was 114.
Preparation Example 9
900 g of ethyl acetate were charged to a stirred apparatus and,
with stirring and in a stream of nitrogen, heated to 77.degree. C.
Then, Feed 1, consisting of 270 g of N-vinylpyrrolidone, 30 g of
1-vinylimidazole and 0.3 g of N,N'-divinylethyleneurea, was metered
in over 3 hours, and Feed 2, consisting of 3 g of
2,2'-azobis(2-methylbutyronitrile) in 80 g of ethyl acetate, was
metered in over 4 hours. The mixture was then stirred for a further
2 hours and cooled to room temperature, and 36 g of dimethyl
sulfate were added thereto. The mixture is then stirred for half an
hour at room temperature and for a further 2 hours at 70.degree. C.
The resulting powder was filtered off and dried. The K value of an
aqueous solution of the polymer was 125.
Preparation Example 10
440 g of water were charged to a stirred apparatus and, with
stirring and in a stream of nitrogen, heated to 60.degree. C. Then,
Feed 1, consisting of 144 g of N-vinylpyrrolidone, 16 g of
3-methyl-1-vinylimidazolium methylsulfate, 1.4 g of tetraethylene
glycol diacrylate and 100 g of water, was metered in over 2 hours,
and Feed 2, consisting of 0.8 g of
2,2'-azobis(2-amidino-propane)dihydrochloride in 50 g of water, was
metered in over 3 hours. Following the addition of Feed 2, the
mixture was stirred for a further 3 hours at 70.degree. C. In order
to keep the reaction mixture stirrable, it was diluted with a total
of 1200 g of water as required. This gave a colorless
high-viscosity polymer solution with a solids content of 8.5% and a
K value of 95.
Preparation Example 11
550 g of water were charged to a stirred apparatus and, with
stirring and in a stream of nitrogen, heated to 60.degree. C. Then,
Feed 1, consisting of 102 g of N-vinylpyrrolidone, 26 g of
3-methyl-1-vinylimidazolium methylsulfate, 0.8 g of triallylamine
and 100 g of water, was metered in over 2 hours. Feed 2, consisting
of 0.6 g of 2,2'-azobis(2-amidinopropane)dihydrochloride in 50 g of
water, was added to the reaction mixture over 3 hours. Following
the addition of Feed 2, the mixture was stirred for a further 3
hours at 70.degree. C. In order to keep the reaction mixture
stirrable, it was diluted with a total of 1000 g of water as
required. This gave a slightly yellowish high-viscosity polymer
solution with a solids content of 7.0% and a K value of 102.
Preparation Example 12
Preparation Example 11 was repeated, but using 2.2 g of
pentaerythritol triallyl ether instead of triallylamine. This gave
a slightly yellowish high-viscosity polymer solution with a K value
of 95.
Preparation Example 13
440 g of water were charged to a stirred apparatus and, with
stirring and in a stream of nitrogen, heated to 60.degree. C. Then,
Feed 1, consisting of 150 g of N-vinylpyrrolidone, 8 g of
3-methyl-1-vinylimidazolium methylsulfate, 0.6 g of triallylamine
and 100 g of water, was metered in over 2 hours, and Feed 2,
consisting of 0.8 g of 2,2'-azobis(2-amidinopropane)dihydrochloride
in 50 g of water, was metered in over 3 hours. Following the
addition of Feed 2, the mixture was stirred for a further 3 hours
at 70.degree. C. In order to keep the reaction mixture stirrable,
it was diluted with a total of 1200 g of water as required. This
gave a colorless high-viscosity polymer solution with a solids
content of 8.1% and K value of 98.
Preparation Example 14
800 g of cyclohexane, 5 g of sorbitan monooleate and 5 g of
Hypermer B246 (Hypermer B246: polymeric surfactant from ICI) were
charged to a reaction vessel with nitrogen blanketing and heated to
60.degree. C. Feed 1, consisting of 60 g of
3-methyl-1-vinylimidazolium methylsulfate, 140 g of
N-vinylpyrrolidone, 150 g of water and 1.0 g of triallylamine, and
Feed 2, consisting of 0.6 g of
2,2'-azobis(2-amidinopropane)dihydrochloride in 50 g of water, were
metered in over the course of 1 hour. The mixture was then stirred
for a further 6 hours at 60.degree. C. 200 g of cyclohexane were
then added and the water was distilled off azeotropically, and the
polymer was filtered off and dried.
Preparation Example 15
800 g of cyclohexane, 5 g of sorbitan monooleate and 5 g of
Hypermer B246 (Hypermer B246; polymeric surfactant from ICI) were
charged to a reaction vessel with nitrogen blanketing and heated to
60.degree. C. Feed 1, consisting of 20 g of
3-methyl-1-vinylimidazolium methylsulfate, 180 g of
N-vinylpyrrolidone, 150 g of water and 0.5 g of triallylamine, was
metered in over the course of 1 hour, and Feed 2, consisting of 1.2
g of 2,2'-azobis(2-amidino-propane)dihydrochloride in 70 g of
water, was metered in over the course of 4 hours. The mixture was
then stirred for a further 3 hours at 60.degree. C. 200 g of
cyclohexane were then added, and the water was distilled off
azeotropically, and the polymer was filtered off and dried.
Preparation Example 16
400 g of water, 100 g of N-vinylpyrrolidone, 11 g of
3-methyl-1-vinylimidazolium methylsulfate and 0.4 g of
triallylamine were charged to a stirred apparatus and, with
stirring and in a stream of nitrogen, heated to 60.degree. C. Then,
Feed 1, consisting of 0.6 g of
2,2'-azobis(2-amidinopropane)dihydrochloride in 50 g of water, was
added to the reaction mixture over 3 hours, and the mixture was
diluted with 1000 g of water. The mixture was then stirred for a
further 3 hours at 80.degree. C. This gave a colorless,
high-viscosity polymer solution with a solids content of 7.6% and K
value of 110.
Preparation Example 17
In a reaction vessel 500 g of cyclohexane, 12 g of sorbitan
monooleate, 6 g of Hypermer B246 (Hypermer B246: polymeric
surfactant from ICI) and an aqueous phase comprising 150 g of
3-methyl-1-vinylimidazolium methylsulfate, 150 g of
vinylpyrrolidone, 0.75 g of 2,2'-azobis(2-amidinopropane)
dihydrochloride, 360 g of water and 0.6 g of divinylethyleneurea
were polymerized for 6 h at 70.degree. C. The water was then
distilled off azeotropically, and the polymer was filtered off and
dried.
Preparation Example 18
In a reaction vessel, 200 g of Mygliol (caprylic/capric
triglycerides from Huls AG), 12 g of sorbitan monooleate, 6 g of
Hypermer B246 (ICI) and an aqueous phase comprising 333 g of
vinylimidazolium methylsulfate, 150 g of vinylpyrrolidone, 0.75 g
of 2,2'-azobis(2-amidinopropane) dihydrochloride, 186 g of water
and 0.6 g of divinylethyleneurea were polymerized for 6 h at
70.degree. C.
Preparation Example 19
500 g of water were charged to a stirred apparatus and heated to
60.degree. C. Then, Feed 1, consisting of 125 g of vinylimidazole,
48 g of acrylic acid, 42 g of NaOH (50% strength aqueous solution),
0.8 g of triallylamine and 500 g of water, and Feed 2, consisting
of 1.25 g of 2,2'-azobis(2-amidinopropane)dihydrochloride and 200 g
of water, were added over 4 h. The internal temperature was then
increased to 70.degree. C., 1.25 g of 2,2'-azobis(2-amidinopropane)
dihydrochloride in 78 g of water were added over the course of 1 h,
and then the mixture was stirred for a further 1 h at 70.degree. C.
In order to keep the reaction mixture stirrable, it was diluted
with a total of 1200 g of water as required. This gave a slightly
yellowish polymer solution with a solids content of 7.8% and a K
value of 110.
Preparation Example 20
Preparation Example 19 was repeated, but using 125 g of
3-methyl-1-vinylimidazolium methylsulfate instead of 125 g of
1-vinylimidazole. This gave a slightly yellowish polymer solution
with a solids content of 7.8% and a K value of 105.
B APPLICATION EXAMPLES
Application Example 1
Skin Cream
Firstly, a water/oil cream emulsion (skin cream A) was prepared in
accordance with the following recipe:
TABLE-US-00002 % by Additive weight Cremophor A 6 Ceteareth-6 and
stearyl alcohol 2.0 Chremophor A 25 Ceteareth-25 2.0 Lanette O
cetearyl alcohol 2.0 Imwitor 960 K glyceryl stearate SE 3.0
Paraffin oil 5.0 Jojoba oil 4.0 Luvitol EHO cetearyl octanoate 3.0
ABIL 350 dimethicone 1.0 Amerchol L 101 mineral oil and lanolin
alcohol 3.0 Veegum Ultra magnesium aluminum silicate 0.5
1,2-Propylene glycol propylene glycol 5.0 Abiol imidazolindinylurea
0.3 Phenoxyethanol 0.5 D-Panthenol USP 1.0 Polymer (Preparation
Example 11) 0.5 Water ad 100
Two comparison creams were prepared in the same way:
Skin cream B (without polymer additive)
Skin cream C (polymer according to the invention replaced by the
same amount of an uncrosslinked copolymer of 30 mol % of
vinylimidazolium chloride and 70 mol % of N-vinylpyrrolidone)
Using these skin creams A, B and C, the following comparative tests
1 and 2 were carried out to assess the feel on the skin.
100 .mu.l of the emulsion were distributed uniformly on the back of
the hand, and the feel on the skin was tested subjectively after a
contact time of 30 minutes. In each case two emulsions were
compared with one another (right/left hand). Each of the tests was
carried out by ten subjects.
Scale of Grades:
2 (markedly softer than comparison cream)
1 (somewhat softer than comparison cream)
0 (equal)
-1 (somewhat rougher than comparison cream)
-2 (markedly more rough than comparison cream
Result of comparison test 1 (comparison of skin cream A and
comparison cream B):
TABLE-US-00003 Grade No. of subjects 2 5 1 4 0 1 -1 -- -2 --
Result of comparison test 2 (comparison of skin cream A and
comparison cream C):
TABLE-US-00004 Grade No. of subjects 2 3 1 5 0 2 -1 -- -2 --
Application Example 2
Shower Gel
A shower gel formulation according to the invention (shower gel A)
was firstly prepared in accordance with the following recipe:
TABLE-US-00005 % by Additives weight Texapon NSO sodium laureth
sulfate 40.0 Tego Betaine L7 cocamidopropylbetaine 5.0 Plantacare
2000 decylglucoside 5.0 Perfume 0.2 Polymer as in Preparation
Example 11 0.2 Euxyl K 100 benzyl alcohol, methyl- 0.1
chlorisothiazolinone, methyl- isothiazolinone D-Panthenol USP 0.5
Citric acid (pH 6-7) q.s. NaCl 2.0 Water ad 100
Three comparison shower gels were prepared in the same manner:
Shower gel B: (copolymer according to the invention replaced by the
same amount of the uncrosslinked polymer polyquaternium-16)
Shower gel C: (copolymer according to the invention replaced by the
same amount of cationically modified hydroxyethylcellulose)
Shower gel D: (without polymer addition)
Using the shower gels A, B, C and D, the following comparison test
3 was carried out to determine the foam creaminess:
2.0 g of each of the abovementioned formulations was placed into
the palm of the left hand, lathered using tap water and, after
rubbing between both hands for 1 minute, the feel of the foam in
the palms of the hands was assessed:
Grade 1: very creamy
Grade 2: creamy
Grade 3: flat/lacking substance
Result of Comparison test 3 (mean value of the rating by 10
subjects):
TABLE-US-00006 Shower gel Mean value from 10 subjects A 1.3 B 2.8 C
2.1 D 2.8
Application Example 3
Moisturizing Formulation
Formulation A
TABLE-US-00007 % by Additive weight a) Cremophor A6 Ceteareth-6 and
stearyl alcohol 2.0 Cremophor A25 Ceteareth-25 2.0 Paraffin oil
(viscous) 10 Lannette O cetearyl alcohol 2.0 Stearic acid 3.0
Nip-Nip methylparaben/propylparaben 70:30 0.5 Abiol
imidazolidinylurea 0.5 b) Polymer (Preparation Example 8) 3.0 Water
ad 100.0
The two phases were heated to 80.degree. C., phase a) was fed into
b) and the mixture was homogenized and stirred until cold and then
adjusted to pH 6 with 10% strength aqueous NaOH solution.
In the same manner, a comparison cream (formulation B) without
polymer additive was prepared.
Using the formulations A and B, a test was carried out on eight
subjects. For this, each of the formulations was applied in an
amount of 2 mg/cm.sup.2 to the forearm of the subjects. After 30
min the moisture content of the skin was determined using a
corneometer CM 825 (Khazaka & Courage). After applying
formulation A a mean value of 45 corneometer units was measured,
and for formulation B a mean value of 35.
Application Example 4
O/W Cream for Moisturizing the Skin
TABLE-US-00008 % by Additive weight Glycerol monostearate 2.0 Cetyl
alcohol 3.0 Paraffin oil, subliquidum 15.0 Vaseline 3.0
Caprylic/capric triglyceride 4.0 Octyldodecanol 2.0 Hydrogenated
coconut fat 2.0 Cetyl phosphate 0.4 Polymer (Preparation Example 6)
3.0 Glycerol 3.0 Sodium hydroxide q.s. Perfume oil q.s.
Preservative q.s. Water ad 100
Application Example 5
O/W Lotion
TABLE-US-00009 % by Additive weight Stearic acid 1.5 Sorbitan
monostearate 1.0 Sorbitan monooleate 1.0 Paraffin oil, subliquidum
7.0 Cetyl alcohol 1.0 Polydimethylsiloxane 1.5 Glycerol 3.0 Polymer
(Preparation Example 17) 0.5 Perfume oil q.s. Preservative q.s.
Water ad 100
Application Example 6
W/O Cream
TABLE-US-00010 % by Additive weight PEG-7 hydrogenated castor oil
4.0 Wool wax alcohol 1.5 Beeswax 3.0 Triglyceride, liquid 5.0
Vaseline 9.0 Ozokerite 4.0 Paraffin oil, subliquidum 4.0 Glycerol
2.0 Polymer (Preparation Example 4) 2.0 Magnesiumsulfate*7H.sub.2O
0.7 Perfume oil q.s. Preservative q.s. Water ad 100
Application Example 7
Hydrogel for Skincare
TABLE-US-00011 % by Additive weight Polymer (Preparation Example
17) 3.0 Sorbitol 2.0 Glycerol 3.0 Polyethylene glycol 400 5.0
Ethanol 1.0 Perfume oil q.s. Preservative q.s. Water ad 100
Application Example 8
Hydrodispersion Gel
TABLE-US-00012 % by Additive weight Polymer (Preparation Example
17) 3.0 Sorbitol 2.0 Glycerol 3.0 Polyethylene glycol 400 5.0
Triglyceride, liquid 2.0 Ethanol 1.0 Perfume oil q.s. Preservative
q.s. Water ad 100
Application Example 9
Liquid Soap
TABLE-US-00013 % by Additive weight Coconut fatty acid, potassium
salt 15 Potassium oleate 3 Glycerol 5 Polymer (Preparation Example
14) 2 Glycerol stearate 1 Ethylene glycol distearate 2 Specific
additives, complexing agents, fragrances, q.s. Water ad 100
Application Example 10
Bodycare Cream
TABLE-US-00014 % by Additive weight Cremophor A6 Ceteareth-6 and
stearyl alcohol 2.0% Cremophor A 25 Ceteareth-25 2.0% Grape (Vitis
vinifera) seed oil 6.0% Glyceryl stearate SE 3.0% Cetearyl alcohol
2.0% Dimethicon 0.5% Luvitol EHO Cetearyloctanoate 8.0% Oxynex 2004
propylene glycol, BHT, ascorbyl 0.1% palmitate, glyceryl stearate,
citric acid Preservative q.s. 1,2-Propylene glycol USP 3.0%
Glycerol 2.0% EDTA BD 0.1% D-Panthenol USP 1.0% Water ad 100
Polymer (Preparation Example 11) 1.5% Tocopheryl acetate 0.5%
The formulation had a pH of 6.8. The viscosity (Brookfield RVT,
23.degree. C.) was 32.000 mPas.
* * * * *